KR20240004763A - Aliphatic copolyamide composition - Google Patents

Abstract

a) greater than 50% to 99% by weight of at least one aliphatic copolyamide as component A), wherein the total weight% of components A and B is 100% by weight; b) a polymer blend comprising from 1% to less than 50% by weight of at least one semi-crystalline, semi-aromatic or aromatic polyamide as component B, a thermoplastic molding composition comprising said polymer blend and at least one further substance C), Methods for making the polymer blend and the thermoplastic molding composition, uses of the polymer blend and the thermoplastic molding composition for the production of molded and extruded parts, and molded and extruded parts made from the polymer blend or the thermoplastic molding composition.

Description

Aliphatic copolyamide composition

explanation

The present invention relates to polymer blends comprising at least one aliphatic copolyamide and at least one semicrystalline, semiaromatic or aromatic polyamide, thermoplastic molding compositions comprising the polymer blend and at least one additional material, and moldings. and the use of polymer blends or thermoplastic molding compositions for the production of extruded parts.

The aliphatic copolyamide PA 6/6.36 can be derived through copolymerization of caprolactam, HMD and aliphatic C36-dicarboxylic acid. PA 6/6.36 is based on partially renewable sources, has a lower humidity absorption compared to standard polyamides such as PA6 or PA66, and exhibits excellent resistance to all but aqueous media such as salt solutions. PA 6/6.36 is used for foil and sheet extrusion. However, aliphatic copolyamides appear to be sticky, which can cause problems during injection molding and pipe extrusion processes. Additionally, aliphatic copolyamides appear to lose stiffness during conditioning in standard atmospheres.

The object underlying the present invention is to provide a polyamide composition having the advantageous properties of aliphatic copolyamides, especially copolyamide PA 6/6.36, but with a superior performance profile, for example higher stiffness in the conditioned state. These compositions are particularly suitable for molding processes such as injection molding and pipe extrusion.

By providing a polymer blend comprising an aliphatic copolyamide and a semi-crystalline, semi-aromatic or aromatic polyamide, a polyamide compound based on a polymer blend comprising a non-semi-crystalline semi-aromatic or aromatic polyamide and an aliphatic copolyamide In comparison, polyamide compounds are obtained which have an excellent performance profile and are very suitable for injection molding and pipe extrusion processes.

Blends of aliphatic polyamides and aromatic polyamides are known.

Xanthos et al., Journal of Applied Polymer Science, Vol. 62, 1167-1177 (1996) describe polyamide 6 (N6) and amorphous aromatic polyamide PA6I/6T (Zytel-330 (2-330)) ( Blends of AmArPA) are described.

Blends of various compositions were extrusion compounded with impact modified reactive elastomers and injection molded. The relationship between blend morphology, blend component structure and reactivity, and processing conditions with ultimate properties is discussed.

Huang et al. (Polymer 47 (2006) 624-638) study the distribution of impact modifiers in blends of polyamide 6 (nylon 6) and amorphous aromatic polyamide PA6I/6T (Zytel 330) (AmArPA).

WO2007/041723 A1 describes a copolyamide composition for marine umbilicals consisting of aromatic dicarboxylic acids, diamines and aliphatic dicarboxylic acids obtained by copolymerization. Preferred copolyamides comprise repeating units (a) derived from terephthalic acid and hexamethylenediamine and repeating units (b) derived from decanedioic acid and/or dodecanedioic acid and hexamethylenediamine.

WO 2019/057849 A1 relates to heat-resistant polyamide compositions comprising copolyamides and anhydride-functional polymers. Copolyamides include the reaction product of at least one lactam and a monomer mixture. The monomer mixture comprises at least one C ₃₂ - C ₄₀ -dimeric acid, and at least one C ₄ - C ₁₂ -diamine.

US 2015/344686 relates to prepregs capable of providing fiber-reinforced composite materials that are stable under a wide range of forming conditions and exhibit excellent interlaminar fracture toughness and impact resistance.

WO 2021/003047 A1 relates to prepregs that can be cured/molded to form aerospace composite parts.

None of WO 2019/057849 A1, US 2015/344686 and WO 2021/003047 A1, in addition to more than 50% by weight of at least one aliphatic copolyamide, at least 1% by weight of at least one semi-crystalline polyamide which is at the same time semi-aromatic or aromatic. It does not disclose a blend containing.

However, polymer blends of aliphatic polyamides and amorphous aromatic polyamides disclosed in the prior art do not achieve the above-mentioned objectives in a sufficient manner.

The object is achieved according to the invention by a polymer blend comprising:

a) more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A);

b) from 1% to less than 50% by weight of at least one semi-crystalline, semi-aromatic or aromatic polyamide as component B;

where the total weight percent of components A and B is 100 weight percent.

The invention also relates to a thermoplastic molding composition comprising a polymer blend and at least one additional substance C.

The present invention also relates to a method of mixing component A and component B to prepare a polymer blend.

The invention also relates to the use of these polymer blends or these thermoplastic molding compositions for producing molded articles, sheets, foils, tubes and pipes of any type.

The invention also relates to molded articles, sheets, foils, tubes or pipes made from these polymer blends or these thermoplastic molding compositions.

According to the present invention, it has been found that the above-mentioned objects are achieved by a combination of aliphatic copolyamides with semi-crystalline, semi-aromatic or aromatic polyamides.

The inventive blends and inventive thermoplastic molding compositions are characterized in particular by one or more of the following properties: high stability to zinc chloride and blue addition, high heat distortion temperature, high tensile modulus in the dry and conditioned state, conditioning. High stiffness in the wet state, low moisture absorption and high barrier to fuel. The inventive blends demonstrate improved processing properties in pipe and sheet extrusion and injection molding processes. Through the blend approach, the material can be easily demolded from the injection molding machine and shows little tendency to stick to the nozzle compared to pure aliphatic copolyamides.

The inventive blends and inventive thermoplastic molding compositions have a wide range of applications, especially in the field of engineering plastics, especially automotive, in contact with fluids such as cooling fluids, brake and clutch fluids, chemicals (plus blue), fuels and/or salts. In industry, for example, extruded tubes (e.g. fluid pipes for fuel or cooling fluids in automobiles), mandrels and injection molded articles such as functional parts for engine sensors (e.g. wheel speed sensors), pumps, connectors or Useful in injection or extrusion parts of fuel cells.

blend

The amount of component A) in the blends of the invention is greater than 50 to 99% by weight, preferably 55 to 97% by weight and more preferably 60 to 95% by weight.

The amount of component B) in the blends of the invention is from 1 to less than 50% by weight, preferably from 3 to 45% by weight, more preferably from 5 to 40% by weight.

The total weight percent of component A and component B is 100 weight percent.

Preferably, component A) forms a continuous phase.

The weight ratio of component A) to component B) is preferably 1.1:1 to 15:1, more preferably 1.3:1 to 12:1, most preferably 1.5:1 to 10:1, especially 1.7:1. It is 9:1.

Component B)

Component B) is at least one semi-crystalline, semi-aromatic or aromatic polyamide. Suitable semi-crystalline, semi-aromatic or aromatic polyamides are known in the art. Preferably, the at least one semi-crystalline polyamide of component B is a semi-aromatic and/or copolyamide, and more preferably, the at least one polyamide of component B is a semi-crystalline, semi-aromatic copolyamide. Suitable semi-crystalline, semi-aromatic copolyamides are disclosed, for example, in EP 0 299 222 A, EP 0 667 367 A and US 2012/0245283.

Generally, semi-crystalline, semi-aromatic copolyamides are copolymers made by condensing aliphatic amides, such as caprolactam and/or hexamethylene diamine, with aromatic dicarboxylic acids or acid derivatives, such as terephthalic acid and/or isophthalic acid, i.e., these poly Amides are partially aromatic polyamides.

More preferably, component B) is at least one semi-crystalline, semi-aromatic polyamide containing repeating units of hexamethylenediamine and terephthalic acid. Preferably, component B) contains 45 to 95% by weight, more preferably 60 to 80% by weight and most preferably 65 to 75% by weight of repeating units of hexamethylenediamine and terephthalic acid. The remainder may be aliphatic polyamide repeat units such as caprolactam or hexamethylene adipamide, or semi-aromatic repeat units such as polyamide-6I.

Preferably, component B) has a viscosity number VZ of 60 to 200 ml/g, more preferably 70 to 140 ml/g.

In a further preferred embodiment, the at least one polyamide of component B has a melting point above 250°C.

Most preferably, the at least one thermoplastic semi-aromatic semi-crystalline polyamide B) is selected from polyamide-6T/6, polyamide-6T/66, polyamide-6T/6I and mixtures thereof.

Component A)

Component A) is at least one aliphatic copolyamide. Suitable aliphatic copolyamides are known in the art.

Preferably, the aliphatic copolyamide of component A has a melting point below 220°C.

More preferably, the at least one copolyamide of component A) is produced by polymerization of the following components:

A') 15% to 84% by weight of at least one lactam,

B') 16% to 85% by weight of monomer mixture (M) comprising the following components:

B1') at least one C ₃₂ -C ₄₀ -dimer acid and

B2') at least one C ₄ -C ₁₂ diamine,

Wherein the weight percentages of components A') and B') are based in each case on the sum of the weight percentages of components A') and B').

In the context of the present invention, the terms “component A')” and “at least one lactam” are used synonymously and therefore have the same meaning.

The same applies to the terms “component B’)” and “monomer mixture (M)”. These terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.

According to the invention, at least one copolyamide is prepared by polymerization of 15 to 84% by weight of component A') and 16 to 85% by weight of component B'), preferably 40 to 83% by weight of component A'. ) and 17 to 60% by weight of component B'), particularly preferably by polymerization of 60 to 80% by weight of component A') and 20 to 40% by weight of component B'), wherein The weight percentages of components A') and B') are based on the sum of the weight percentages of components A') and B', respectively.

The sum of the weight percent of components A') and B') is preferably 100 weight percent.

It will be understood that the weight percentages of components A') and B') relate to the weight percentages of components A') and B') before polymerization, i.e. when components A') and B') have not yet reacted with each other. During the polymerization of components A') and B'), the weight ratio of components A') and B') can optionally be varied.

At least one copolyamide of component A) is produced by polymerization of components A') and B'). The polymerization of components A') and B') is known to the person skilled in the art. The polymerization of components A') and B') is typically a condensation reaction. During the condensation reaction, component A') reacts with components B1') and B2'), which are present in component B'), and optionally with component B3') described below, which may also be present in component B'). This results in the formation of amide bonds between the individual components. During polymerization, component A') is typically at least partially in open chain form, i.e. in the form of amino acids.

The polymerization of components A') and B') can take place in the presence of a catalyst. Suitable catalysts include all catalysts known to the person skilled in the art that catalyze the polymerization of components A') and B'. Such catalysts are known to those skilled in the art. Preferred catalysts are phosphorus compounds, e.g. Sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenyl phosphite.

Polymerization of components A') and B') forms at least one copolyamide, thus comprising units derived from component A') and units derived from component B'. Units derived from component B') include units derived from components B1') and B2') and optionally units derived from component B3').

Polymerization of components A') and B') forms the copolyamide as a copolymer. The copolymer may be a random copolymer. It may likewise be a block copolymer.

In the block copolymer, blocks of units derived from component B') and blocks of units derived from component A') are formed. These appear in an alternating order. In random copolymers, units derived from component A') are alternating with units derived from component B'). This interaction is random. For example, two units derived from component B') may be followed by one unit derived from component A'), followed by a unit derived from component B'), and then Units comprising three units derived from component A') may follow.

The production of at least one copolyamide preferably includes the following steps:

I) polymerizing components A') and B') to obtain at least the first copolyamide,

II) pelletizing the at least one first copolyamide obtained in step I) to obtain at least one pelletized copolyamide,

III) extracting the at least one pelletized copolyamide obtained in step II) with water to obtain at least one extracted copolyamide,

IV) drying the at least one extracted copolyamide obtained in step III) at temperature TT to obtain at least one copolyamide,

IV) drying the at least one extracted copolyamide obtained in step III) at temperature (TT) to obtain at least one copolyamide.

The polymerization in step I) can be carried out in any reactor known to the person skilled in the art. Stirred tank reactors are preferred. It is also possible to improve reaction management by using auxiliaries known to those skilled in the art, for example anti-foaming agents such as polydimethylsiloxane (PDMS).

In step II), the at least one first copolyamide obtained in step I) can be pelletized by any method known to the person skilled in the art, for example by strand pelletization or underwater pelletization.

The extraction in step III) can be performed by any method known to those skilled in the art.

During the extraction in step III), the by-products typically formed during the polymerization of components A') and B') of step I) are extracted from at least one pelletized copolyamide.

In step IV), the at least one extracted copolyamide obtained in step III) is dried. Drying processes are known to those skilled in the art. According to the invention, the at least one extracted copolyamide is dried at temperature T _T . The temperature (T _T ) is preferably higher than the glass transition temperature (T _G(C) ) of the at least one copolyamide and lower than the melting temperature (T _{M (C)} ) of the at least one copolyamide.

Drying in step IV) is typically carried out for a period in the range from 1 to 100 hours, preferably in the range from 2 to 50 hours, particularly preferably in the range from 3 to 40 hours.

It is believed that drying in step IV) further increases the molecular weight of the at least one copolyamide.

The at least one copolyamide of component A) without addition of component B) typically has a glass transition temperature (T _G(C) ). The glass transition temperature (T _G(C) ), as determined according to ISO 11357-2:2014, is for example in the range from 20° C. to 50° C., preferably in the range from 23° C. to 50° C., particularly preferably 25° C. It ranges from ℃ to 50℃.

In the context of the present invention, the glass transition temperature (T _G(C) ) of the at least one copolyamide is based on the glass transition temperature of the dry copolyamide (T _G(C) ) according to ISO 11357-2:2014. Do it as

In the context of the present invention, “dry” means that at least one copolyamide is present in an amount of less than 1% by weight, preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight, based on the total weight of the at least one copolyamide. It should be understood to mean that it includes water. “Dry” should be understood to mean that, more preferably, the at least one copolyamide is free of water, and more preferably, the at least one copolyamide is free of solvent.

Additionally, the at least one copolyamide typically has a melting temperature (T _M(C) ). The melting temperature (T _M(C) ) of the at least one copolyamide, as determined according to ISO 11357-3:2014, is for example in the range from 150 to 210° C., preferably in the range from 160 to 205° C., especially Preferably it is in the range of 160 to 200°C.

The at least one copolyamide generally has a viscosity number (VN _{( C)} has ).

The viscosity number (VN _(C) ) of the at least one copolyamide is 160 to 290 mL/g, as determined in a 0.5% by weight solution of the at least one copolyamide in a mixture of phenol/o-dichlorobenzene in a 1:1 weight ratio. It is preferable that it is in the range, especially preferably in the range of 170 to 280 mL/g.

Component A')

According to the invention, component A') is at least one lactam.

In the context of the present invention, “at least one lactam” is understood to mean exactly one lactam or a mixture of two or more lactams.

Lactams are known per se to those skilled in the art. According to the invention, lactams having 4 to 12 carbon atoms are preferred.

In the context of the present invention, “lactam” should be understood to mean a cyclic amide having preferably 4 to 12 carbon atoms in the ring, particularly preferably 5 to 8 carbon atoms.

Suitable lactams are, for example, 3-aminopropanolactam (propio-3-lactam; β-lactam; β-propiolactam), 4-aminobutanolactam (butyro-4-lactam; γ-lactam) ; γ-butyrolactam), aminopentanolactam (2-piperidinone; δ-lactam; δ-valerolactam), 6-aminohexanolactam (hexano-6-lactam; ε-lactam; ε-capro) lactam), 7-aminoheptanolactam (heptano-7-lactam; ζ-lactam; ζ-heptanolactam), 8-aminooctanolactam (octano-8-lactam; η-lactam; η-octano lactam), 9-aminononanolactam (nonano-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam (decano-10-lactam; ω-decanolactam), 11 - is selected from the group consisting of aminoundecanolactam (undecano-11-lactam, ω-undecanolactam) and 12-aminododecanolactam (dodecano-12-lactam; ω-dodecanolactam).

Accordingly, the present invention also provides that component A') is 3-aminopropanolactam, 4-aminobutanolactam, 5-aminopentanolactam, 6-aminohexanolactam, 7-aminoheptanolactam, 8-aminooctano. Provided is a process selected from the group consisting of lactams, 9-aminononanolactam, 10-aminodecanolactam, 11-aminundecanolactam and 12-aminododecanolactam.

Lactams may be unsubstituted or at least monosubstituted. When at least a monosubstituted lactam is used, the nitrogen atom and/or its ring carbon atom are independently selected from the group consisting of C ₁ to C ₁₀ alkyl, C ₅ to C ₆ cycloalkyl, and C ₅ to C ₁₀ aryl. It may have 1, 2 or more substituents.

Suitable C ₁ - to C ₁₀ -alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. Suitable C ₅ - to C ₆ -cycloalkyl substituents are, for example, cyclohexyl. Preferred C ₅ - to C ₁₀ -aryl substituents are phenyl or anthranyl.

Preference is given to using unsubstituted lactams, preferred being γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam). Particularly preferred are δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam), and ε-caprolactam is particularly preferred.

Monomer mixture (M)

According to the invention, component B') is a monomer mixture (M). The monomer mixture (M) comprises components B1'), at least one C ₃₂ -C ₄₀ dimer acid, and B2'), at least one C ₄ -C ₁₂ diamine.

In the context of the present invention, monomer mixture (M) should be understood to mean a mixture of two or more monomers, where at least components B1') and B2') are present in the monomer mixture (M).

In the context of the present invention, the terms “component B1')” and “at least one C ₃₂ -C ₄₀ dimer acid” are used synonymously and therefore have the same meaning. The same applies to the terms “component B2')” and “at least one C ₄ -C ₁₂ diamine”. These terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.

The monomer mixture (M) is in each case based on the sum of the mole percentages of components B1') and B2'), preferably based on the total amount of substances in the monomer mixture (M), for example from 45 to 55 mol. % of component B1') and component B2') in the range of 45 to 55 mole %.

Component B') is in each case based on the sum of the mole % of components B1') and B2'), preferably in the range of 47 to 53 mole %, based on the total amount of substances of component B'). and B2') in the range of 47 to 53 mol%.

Component B') is in each case based on the sum of the mole % of components B1') and B2'), preferably in the range of 49 to 51 mole %, based on the total amount of substances of component B'). and component B2') in the range from 49 to 51 mol%.

The mole % of components B1') and B2') present in component B') are typically added to 100 mole %.

Component B') may further comprise at least one C ₄ -C ₂₀ diacid, which is component B3').

In the context of the present invention, the terms “component B3')” and “at least one C ₄ -C ₂₀ diacid” are used synonymously and therefore have the same meaning.

If component B') additionally comprises component B3'), then component B') comprises component B1') in the range from 25 to 54.9 mol%, in each case based on the total amount of substances of component B'), from 45 to 55. Preference is given to comprising component B2') in the mole percent range and component B3') in the mole percent range from 0.1 to 25 mole percent.

Component B') is followed by component B1') in the range from 13 to 52.9 mol%, component B2)' in the range from 47 to 53 mol% and in the range from 0.1 to 13 mol%, in each case based on the total amount of substances of component B'). It is particularly preferred if it contains component B3').

Component B') is followed by component B1') ranging from 7 to 50.9 mol%, component B2') ranging from 49 to 51 mol% and ranging from 0.1 to 7 mol%, in each case based on the total amount of substances of component B'). It is most preferred if it contains component B3').

If component B') additionally comprises component B3'), the mole % of components B1'), B2') and B3') are typically added to 100 mole %.

The monomer mixture (M) may additionally include water.

Components B1') and B2') and optionally B3') of component B') can react with each other to give the amide. These reactions are known per se to those skilled in the art. Accordingly, component B') may comprise components B1'), B2') and optionally B3') in fully reacted, partially reacted or unreacted form. It is preferred if component B') comprises components B1'), B2') and optionally B3') in unreacted form.

Therefore, in the context of the present invention, "in unreacted form" means that component B1') is present as at least one C ₃₂ -C ₄₀ dimer acid and component B2') is present as at least one C ₄ -C ₁₂ -diamine. is present, and optionally component B3') is to be understood as meaning present as at least one C ₄ -C ₂₀ diacid.

If components B1') and B2') and optionally B3') are at least partially reacted, then components B1') and B2') and optionally B3') are therefore at least partially in amide form.

Component B1')

According to the invention, component B1') is at least one C ₃₂ -C ₄₀ dimer acid.

In the context of the present invention, “at least one C ₃₂ -C ₄₀ dimer acid” means exactly one C ₃₂ -C ₄₀ -dimer acid or a mixture of two or more C ₃₂ -C ₄₀ dimer acids. It must be understood.

Dimeric acids are also referred to as dimer fatty acids. C ₃₂ -C ₄₀ dimer acids are known per se to those skilled in the art and are typically produced by dimerization of unsaturated fatty acids. This dimerization can be catalyzed, for example, by argillaceous earth.

Unsaturated fatty acids suitable for the production of at least one C ₃₂ -C ₄₀ dimer are known to the person skilled in the art and are, for example, unsaturated C ₁₆ -fatty acids, unsaturated C ₁₈ fatty acids and unsaturated C ₂₀ fatty acids.

Therefore, it is preferred if component B1') is produced from unsaturated fatty acids selected from the group consisting of unsaturated C ₁₆ fatty acids, unsaturated C ₁₈ fatty acids and unsaturated C ₂₀ fatty acids, where unsaturated C ₁₈ fatty acids are particularly preferred.

A suitable unsaturated C ₁₆ fatty acid is, for example, palmitoleic acid ((9Z)-hexadeca-9-enoic acid).

Suitable unsaturated C ₁₈ fatty acids are, for example, petrocelic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca -9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoic acid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid), α-linolenic acid ((9Z,12Z,15Z )-octadeca-9,12,15-trienoic acid), γ-linolenic acid ((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid), calendulic acid ((8E,10E, 12Z)-octadeca-8,10,12-trienoic acid), punic acid ((9Z,11E,13Z)-octadeca-9,11,13-trienoic acid), α-eleostearic acid (( 9Z,11E,13E)-octadeca-9,11,13-trienoic acid) and β-eleostearic acid ((9E,11E,13E)-octadeca-9,11,13-trienoic acid) is selected from the group consisting of Petrocelic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid ((11E Particularly preferred are unsaturated C ₁₈ fatty acids selected from the group consisting of )-octadeca-11-enoic acid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid).

Suitable unsaturated C ₂₀ fatty acids are, for example, gadoleic acid ((9Z)-eicosa-9-enoic acid), ecosenoic acid ((11Z)-eicosa-11-enoic acid), arachidonic acid ((5Z,8Z, 11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and thymnodonic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-penta is selected from the group consisting of ene acids).

Component B1') is particularly preferably at least one C ₃₆ dimer acid.

At least one C ₃₆ dimer acid is preferably produced from an unsaturated C ₁₈ fatty acid. C ₃₆ dimer acids are petroleum acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), Particular preference is given to those produced from C ₁₈ fatty acids selected from the group consisting of vaccenic acid ((11E)-octadeca-11-enoic acid) and linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid).

The production of component B1') from unsaturated fatty acids may form trimer acids, and residues of unconverted unsaturated fatty acids may also remain.

The formation of trimer acids is known to those skilled in the art.

According to the invention, component B1') preferably comprises up to 0.5% by weight of unreacted unsaturated fatty acids and up to 0.5% by weight of trimer acids, especially preferably up to 0.5% by weight, based in each case on the total weight of component B1'). It contains not more than 0.2% by weight of unreacted unsaturated fatty acids and not more than 0.2% by weight of trimer acids.

Therefore, dimer acids (also known as dimerized fatty acids or dimer fatty acids) should be understood generally and in particular in the context of the present invention to mean mixtures resulting by oligomerization of unsaturated fatty acids. They can be produced, for example, by catalytic dimerization of unsaturated fatty acids of plant origin, where the starting materials used are in particular unsaturated C ₁₆ to C ₂₀ fatty acids. Bonding proceeds primarily by the Diels-Alder mechanism, resulting in aliphatic, linear, aliphatic, or cycloaliphatic groups between the carboxyl groups, depending on the number and position of the double bonds of the fatty acid used to generate the dimer acid. A mixture of mainly dimer products with topographic aliphatic and also C ₆ aromatic hydrocarbon groups is produced. Depending on the mechanism and/or any subsequent hydrogenation, the aliphatic radicals may be saturated or unsaturated and the proportion of aromatic groups may also vary. The radicals between the carboxylic acid groups contain, for example, 32 to 40 carbon atoms. Preferably, fatty acids with 18 carbon atoms are used for production, so that the dimer product has 36 carbon atoms. The radicals linking the carboxyl groups of the dimer fatty acid preferably do not contain unsaturated bonds and aromatic hydrocarbon radicals.

Therefore, in the context of the present invention, preference is given to using C ₁₈ fatty acids for production. Particular preference is given to using linolenic acid, linoleic acid and/or oleic acid.

Depending on the reaction management, the oligomerization described above gives a mixture comprising mainly dimer but also trimer molecules and also monomer molecules and other by-products. Purification by distillation is common. Commercial dimer acids generally contain at least 80% by weight of dimer molecules, up to 19% by weight of trimer molecules, and up to 1% by weight of monomer molecules and other by-products.

It is preferred to use dimer acids consisting of at least 90% by weight, preferably at least 95% by weight and very particularly preferably at least 98% by weight of dimer fatty acid molecules.

The proportions of monomer, dimer and trimer molecules and other by-products in the dimer acid can be determined, for example, by gas chromatography (GC). The dimer acid is converted to the corresponding methyl ester by the boron trifluoride method (see DIN EN ISO 5509) before GC analysis.

Therefore, in the context of the present invention, it is a fundamental characteristic of “dimeric acids” that their production involves oligomerization of unsaturated fatty acids. This oligomerization forms the dimer product mainly, i.e. preferably at least 80% by weight, particularly preferably at least 90% by weight, very preferably at least 95% by weight and especially at least 98% by weight. Therefore, the fact that oligomerization predominantly forms dimer products containing exactly two fatty acid molecules justifies this designation, which is common in any case. Accordingly, an alternative expression for the related term “dimeric acid” is “a mixture comprising dimerized fatty acids”.

The dimer acid to be used is available as a commercial product. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976 and Radiacid 0977 from Oleon NV, Pripol 1006, Pripol 1009, Pripol 1012 and Pripol 1013 from Croda, Empol 1008, Empol 1012, Empol 1061 and Empol from BASF SE. ol 1062 , and Unidyme 10 and Unidyme Tl from Arizona Chemical.

Component B1') has an acid number, for example, in the range from 190 to 200 mg KOH/g.

Component B2')

According to the invention, component B2') is at least one C ₄ -C ₁₂ diamine.

“At least one C ₄ -C ₁₂ diamine” in the context of the present invention should be understood to mean exactly one C ₄ -C ₁₂ diamine or a mixture of two or more C ₄ -C ₁₂ diamines.

In the context of the present compounds, “C ₄ -C ₁₂ diamine” should be understood to mean aliphatic and/or aromatic compounds having 4 to 12 carbon atoms and 2 amino groups (-NH ₂ groups). The aliphatic and/or aromatic compounds may be unsubstituted or further at least monosubstituted. If the aliphatic and/or aromatic compounds are further at least mono-substituted, they may have one, two or more substituents that do not participate in the polymerization of components A') and B'. Such substituents are, for example, alkyl or cycloalkyl substituents. These are known per se to those skilled in the art. It is preferred that at least one C ₄ -C ₁₂ diamine is unsubstituted.

Suitable components B2') are, for example, 1,4-diaminobutane (butane-1,4-diamine; tetramethylenediamine; putrescine), 1,5-diaminopentane (pentamethylenediamine; pentane- 1,5-diamine; cadaverine), 1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine), 1,7-diaminoheptane, 1,8-diaminoctane, 1,9 - Consisting of diaminononane, 1,10-diaminodecane (decamethylenediamine), 1,11-diaminoundecane (undecamethylenediamine), and 1,12-diaminododecane (dodecamethylenediamine) selected from the group.

Preference is given if component B2') is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.

Component B3')

According to the invention, component B3'), which is optionally present in component B'), is at least one C ₄ -C ₂₀ diacid.

In the context of the present invention, “at least one C ₄ -C ₂₀ diacid” should be understood to mean exactly one C ₄ -C ₂₀ diacid or a mixture of two or more C ₄ -C ₂₀ diacids.

In the context of the present invention, “C ₄ -C ₂₀ diacids” should be understood to mean aliphatic and/or aromatic compounds having 2 to 18 carbon atoms and 2 carboxyl groups (-COOH groups). The aliphatic and/or aromatic compounds may be unsubstituted or further at least monosubstituted. If the aliphatic and/or aromatic compounds are further at least mono-substituted, they may have one, two or more substituents that do not participate in the polymerization of components A') and B'. Such substituents are, for example, alkyl or cycloalkyl substituents. These are known to those skilled in the art. Preferably, at least one C ₄ -C ₂₀ diacid is unsubstituted.

Suitable components B3') are, for example. Butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid) , decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.

Preference is given if component B3') is selected from the group consisting of pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.

Most preferably, the at least one aliphatic polyamide of component A) is ε-caprolactam (as component A'), at least one C ₃₆ dimer acid (as component B1') and hexamethylene diamine (as component B2'). ) is derived from.

The component preferably has a melting point of 190 to 210°C, specifically a melting point of 195 to 200°C, more specifically 196 to 199°C and/or a (polymerized) caprolactam content of 60 to 80% by weight, more It is particularly preferred if it is preferably 65 to 75% by weight, especially 67 to 70% by weight, of PA 6/6.3, with the remainder being PA 6.36 units derived from hexamethylene diamine and C ₃₆ diacids.

Thermoplastic molding composition

The invention also relates to a thermoplastic molding composition comprising the polymer blend according to the invention and at least one additional substance C).

The thermoplastic molding composition preferably comprises:

i) 1 to 99.9% by weight of a polymer blend comprising: and

a) more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A);

b) from 1% to less than 50% by weight of at least one semi-crystalline, semi-aromatic or aromatic polyamide as component B);

wherein the total weight percent of components A) and B) is 100 weight percent;

ii) from 0.1% to 99% by weight of at least one additional substance as component C),

where the weight percent of polymer blend and component C) is 100 weight percent.

The at least one additional substance as component C) is selected from one or more of the following components:

C1) at least one fibrous and/or particulate filler;

C2) at least one impact modifier;

C3) at least one thermoplastic polymer distinct from components A), B), C2) and C4); and

C4) One or more additional additives.

Accordingly, the invention also relates to a thermoplastic molding composition according to the invention comprising as additional substance C) at least one fibrous and/or particulate filler as component C1).

Accordingly, the invention also relates to a thermoplastic molding composition according to the invention comprising as additional substance C) at least one impact modifier as component C2).

Accordingly, the invention also relates to a thermoplastic molding composition according to the invention comprising as further substance C) at least one thermoplastic polymer distinct from components A), B), C2) as component C3) and distinct from optional further additives. It's about.

In one embodiment, the present invention relates to reinforced thermoplastic molding composition TM1 comprising:

i) 35 to 90% by weight, preferably 35 to 70% by weight, more preferably 40 to 60% by weight of a polymer blend comprising:

a) more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A);

b) from 1% to less than 50% by weight of at least one semi-crystalline, semi-aromatic or aromatic polyamide as component B);

wherein the total weight percent of components A) and B) is 100 weight percent;

iia) 10 to 65% by weight, preferably 30 to 65% by weight, more preferably 40 to 60% by weight of at least one fibrous and/or particulate filler as component C1), and

iib) 0 to 30% by weight as component C2), preferably 0 to 20% by weight, more preferably 0 to 10% by weight of at least one impact modifier and/or one or more additional additives as component C4),

where the total weight percent of the polymer blend, components C1), C2) and C4) is 100 weight percent.

If present, the amount of components C2) and/or C4) in the thermoplastic molding composition TM1 is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

In a further embodiment, the invention relates to an impact modified thermoplastic molding composition TM2 comprising:

i) 35 to 90% by weight, preferably 35 to 70% by weight, more preferably 40 to 60% by weight of a polymer blend comprising:

a) more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A);

b) from 1% to less than 50% by weight of at least one semi-crystalline, semi-aromatic or aromatic polyamide as component B);

wherein the total weight percent of components A) and B) is 100 weight percent;

iia) 0 to 65% by weight, preferably 0 to 60% by weight, of at least one fibrous and/or particulate filler as component C1), and

iib) 1 to 25% by weight, preferably 2 to 20% by weight, more preferably 3 to 15% by weight of at least one impact modifier as component C2); and

iic) one or more additional additives as component C4),

where the total weight percent of the polymer blend, components C1), C2) and C4) is 100 weight percent.

If present, the amount of component C4) in the thermoplastic molding composition TM2 is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

In a further embodiment, the invention relates to a blended thermoplastic molding composition TM3 comprising:

i) 1 to 99.9% by weight, preferably 1.2 to 98% by weight, more preferably 1.5 to 90% by weight of a polymer blend comprising:

a) more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A);

b) from 1% to less than 50% by weight of at least one semi-crystalline, semi-aromatic or aromatic polyamide as component B);

wherein the total weight percent of components A) and B) is 100 weight percent;

iia) 0.1 to 99% by weight, preferably 2 to 98.8% by weight, more preferably 10 to 98.5% by weight of at least one thermoplastic as component C3) as distinct from components A), B), C2) and C4) polymer;

iib) 0 to 65% by weight, preferably 0 to 60% by weight, of at least one fibrous and/or particulate filler as component C1), and

iic) 0 to 30% by weight as component C2), preferably 0 to 20% by weight, more preferably 0 to 10% by weight of at least one impact modifier and/or one or more additional additives as component C4),

where the total weight percent of the polymer blend, components C1), C2) and C4) is 100 weight percent.

If present, the amount of components C2) and/or C4) in the thermoplastic molding composition TM3 is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

By blending the blend of the invention with at least one thermoplastic polymer distinct from components A), B), C2) and C4) as component C3), a thermoplastic polymer C3) having a melting point generally lower than that of component B) is obtained. It is possible to achieve blending of component B) of the inventive blend. Direct blending of component B) with thermoplastic polymers C3) having a melting point lower than that of component B) will generally lead to thermal decomposition.

For example, a blend according to the invention (e.g. 30 w% ARLEN® C2000 from Mitsui Chemicals Europe GmbH (ArPA3) in 70 w% Ultramid® Flex F29 from BASF SE (AlCoPA 1)) at 240° C. It is possible to blend with. In contrast, direct blending of homopolymers ArPA3, AlCoPA1 and polypropylene will result in thermal decomposition of polypropylene due to the high melting point of ArPA3 (310°C).

Fibrous or particulate fillers C1) that may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, quartz powder, mica, barium sulfate and feldspar.

Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, with glass fibers of the E glass type being particularly preferred. They can be used as rovings or in the commercially available chopped glass form.

The fibrous filler may have been surface pretreated with a silane compound to improve compatibility with thermoplastic materials.

Suitable silane compounds have the general formula:

In the above formula, the definitions of substituents are as follows:

X is NH ₂ -, , HO-,

n is an integer of 2 to 10, preferably 3 to 4,

m is an integer from 1 to 5, preferably from 1 to 2,

k is an integer of 1 to 3, preferably 1.

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes containing a glycidyl group as substituent X.

The content of the silane compound generally used for surface coating is (based on C1))) 0.01 to 2% by weight, preferably 0.025 to 1.0% by weight, especially 0.05 to 0.5% by weight.

Acicular mineral fillers are also suitable. For the purposes of the present invention, acicular mineral fillers are mineral fillers with strongly developed acicular properties. An example is acicular wollastonite. The mineral preferably has a length to diameter (L/D) ratio of 8:1 to 35:1, preferably 8:1 to 11:1. The mineral filler may optionally have been pretreated with the silane compounds mentioned above, but pretreatment is not essential.

Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and also layered or acicular nanofillers, the amount of which is preferably 0.1 to 10% (based on the thermoplastic molding composition). Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite and laponite. The layered nanofillers are organically modified by prior art methods to provide excellent compatibility with organic binders. Addition of layered or needle-like nanofillers to the nanocomposite of the present invention further increases mechanical strength.

Impact modifiers C2) (sometimes also called elastomeric polymers, elastomers or rubbers) are very generally, preferably, the following monomers: ethylene, C _3-18 α olefins such as propylene, butene, octene, decene or isobutene, butadiene, isoprene. , chloroprene, vinyl acetate, styrene, acrylonitrile and at least two of acrylates and/or methacrylates having 1 to 18 carbon atoms in the alcohol component, this copolymer being, for example, It can be grafted with carboxylic acids or corresponding anhydrides, such as maleic acid or maleic anhydride. Examples include copolymers of maleic anhydride with grafted ethylene and C _3-18 α olefins (as mentioned above), such as maleic anhydride grafted ethylene/octene copolymers and maleic anhydride grafted ethylene/propylene. There are copolymers.

Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pages 392-406, and in the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, UK, 1977).

Some preferred types of these elastomers are described below.

Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers are generally substantially free of residual double bonds, whereas EPDM rubbers may have from 1 to 20 double bonds per 100 carbon atoms.

Examples that may be mentioned for diene monomers for EPDM rubber are conjugated dienes, such as isoprene and butadiene, non-conjugated dienes with 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1, 5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and also al Kenylnorbornene, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methalyl-5-norbornene and 2-isopropenyl-5-norbornene nene, and tricyclodienes such as 3-methyltricyclo[5.2.1.0 ^2,6 ]-3,8-decadiene, and mixtures thereof. 1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubber is preferably 0.5 to 50% by weight, especially 1 to 8% by weight, based on the total weight of the rubber.

EPM rubber and EPDM rubber can also preferably be grafted with reactive carboxylic acids or their derivatives. Examples of these are acrylic acid, methacrylic acid and their derivatives, such as glycidyl (meth)acrylate and also maleic anhydride.

Copolymers of ethylene with acrylic acid and/or methacrylic acid and/or esters of these acids are another group of preferred rubbers. Rubbers may also contain dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, such as esters and anhydrides and/or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers comprising epoxy groups are preferably incorporated into the rubber by adding to the monomer mixture monomers comprising dicarboxylic acid groups and/or epoxy groups and having the general formula I or II or III or IV:

In the above formula, R ¹ to R ⁹ are hydrogen or an alkyl group having 1 to 6 carbon atoms, m is an integer from 0 to 20, g is an integer from 0 to 10, and p is an integer from 0 to 5.

The radicals R ¹ to R ⁹ are preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride and (meth)acrylates containing epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols such as It is tert-butyl acrylate. The latter do not have free carboxy groups, but their behavior is similar to that of free acids and are therefore called monomers with potential carboxy groups.

The copolymer advantageously consists of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers comprising epoxy groups and/or methacrylic acid and/or monomers comprising anhydride groups, the remaining amount being (meth)acrylic. It's a rate.

Particularly preferred are copolymers consisting of:

- 50 to 98% by weight, especially 55 to 95% by weight of ethylene,

- 0.1 to 40% by weight, especially 0.3 to 20% by weight of glycidyl acrylate and/or glycidyl methacrylate, (meth)acrylic acid and/or maleic anhydride, and

- 1 to 45% by weight, especially 5 to 40% by weight of n-butyl acrylate and/or 2-ethylhexyl acrylate;

Here, the total weight percent of the copolymer is 100 weight percent.

Other preferred (meth)acrylates are methyl, ethyl, propyl, isobutyl and tert-butyl esters.

Comonomers that can be used with these are vinyl esters and vinyl ethers.

The ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization at high pressure and elevated temperature. Suitable processes are well known.

Other preferred elastomers are emulsion polymers, the preparation of which is described, for example, in Blackley's monograph "Emulsion Polymerization". Emulsifiers and catalysts that can be used are known per se.

In principle, it is possible to use homogeneously structured elastomers or elastomers with a shell structure. The shell-like structure is determined by the order of addition of the individual monomers. The morphology of the polymer is also influenced by this order of addition.

For the preparation of the rubber fraction of the elastomer, by way of example only, monomers that may be mentioned herein include acrylates, for example n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene. , and also mixtures thereof. These monomers can be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ether, and other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate, or propyl acrylate. .

The soft or rubbery phase of the elastomer (glass transition temperature below 0° C.) may be the core, the outer envelope or the middle shell (for elastomers whose structure has more than two shells). Elastomers with more than one shell may have more than one shell composed of a rubbery phase.

If the structure of the elastomer contains, in addition to the rubber phase, one or more hard components (glass transition temperature greater than 20°C), these are usually the main monomers, such as styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p -It is prepared by polymerizing methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or methyl methacrylate. In addition to these, it is also possible to use relatively small proportions of other comonomers.

In some cases it has proven advantageous to use emulsion polymers with reactive groups on their surfaces. Examples of groups of this type are epoxy, carboxy, latent carboxy, amino and amide groups, and also functional groups that can be introduced by simultaneous use of monomers of the formula:

In the above formula, the substituents can be defined as follows:

R ¹⁰ is hydrogen or C ₁ -C ₄ -alkyl group,

R ¹¹ is hydrogen, a C ₁ -C ₈ -alkyl group or an aryl group, especially phenyl,

R ¹² is hydrogen, C ₁ -C ₁₀ -alkyl group, C ₆ -C ₁₂ -aryl group, or -OR ¹³ ,

R ¹³ is a C ₁ -C ₈ -alkyl group or a C ₆ -C ₁₂ -aryl group which may be optionally substituted with an O-containing group or a N-containing group,

X is a chemical bond, a C ₁ -C ₁₀ -alkylene group, or a C ₆ -C ₁₂ -arylene group, or ego,

Y is O-Z or NH-Z,

Z is a C ₁ -C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene group.

The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups to surfaces.

Other examples that may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates, such as (N-tert-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, ( There are (N,N-dimethylamino)methyl acrylate and (N,N-dimethylamino)ethyl acrylate.

Rubber-like particles may also be cross-linked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and also the compounds described in EP-A 50,265.

It is also possible to use monomers known as graft-linked monomers, i.e. monomers with two or more polymerizable double bonds that react at different rates during polymerization. It is preferred to use compounds of this type in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or reactive groups) polymerizes, for example, significantly more slowly. Different polymerization rates result in a constant proportion of unsaturated double bonds in the rubber. Then, when another phase is grafted onto this type of rubber, at least some of the double bonds present in the rubber react with the graft monomers to form chemical bonds, i.e. the grafted phase has at least some degree of relative affinity to the graft base. It has a chemical bond of

Examples of graft-linked monomers of this type include allyl groups, especially allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate. , and the corresponding monoallyl compounds of these dicarboxylic acids. In addition to these there are a variety of other suitable graft-linked monomers. For further details reference may be made herein, for example to US Pat. No. 4 148 846.

The proportion of these crosslinking monomers in the impact-modifying polymer is generally at most 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.

Some preferred emulsion polymers are listed below. Graft polymers having a core and at least one outer shell and having the structure:

Instead of graft polymers whose structure has more than one shell, it is also possible to use homogeneous, i.e. single-shell elastomers consisting of 1,3-butadiene, isoprene and n-butyl acrylate or their copolymers. These products can also be prepared by simultaneously using cross-linking monomers or monomers with reactive groups.

Examples of preferred emulsion polymers include n-butyl acrylate-(meth)acrylic acid copolymer, n-butyl acrylate/glycidyl acrylate or n-butyl acrylate/glycidyl methacrylate copolymer, n-butyl acrylate. These are graft polymers with an inner core composed of polyethylene or based on butadiene and an outer shell composed of the above-mentioned copolymers, and copolymers of ethylene with comonomers supplying reactive groups.

The described elastomers can also be prepared by other conventional processes, for example suspension polymerization.

Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.

Of course, it is also possible to use mixtures of the rubber types listed above.

As component C3), preferred thermoplastic polymers, as distinct from components A), B), C2) and C4), are polymers with a melting point below 300° C., preferably below 280° C.

Examples of suitable thermoplastic polymers, as component C3), distinct from components A), B), C2) and C4), are preferably selected from:

- C ₂ -C ₁₀ -monoolefins, for example ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C ₂ -C ₁₀ -alkyl esters, vinyl chloride, Vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with an alcohol component of branched and unbranched C ₁ -C ₁₀ -alcohols, Vinyl aromatics, for example, comprising in copolymerized form at least one monomer selected from styrene, acrylonitrile, methacrylonitrile, α,β-ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride. polymer or copolymer;

- polyamides distinct from components A and B, for example amorphous polyamides;

- Homopolymers and copolymers of vinyl acetal;

- polyvinyl ester;

- Polycarbonate (PC);

- polyesters, such as polyalkylene terephthalate, polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA);

- polyether;

- polyether ketone;

- Thermoplastic polyurethane (TPU);

- polysulfide;

- polysulfone;

- polyether sulfone;

- Cellulose alkyl esters;

and mixtures thereof.

Examples include polyolefins, acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-propylene copolymer, ethylene-propylene-diene copolymer (EPDM), polystyrene (PS), styrene-acrylonitrile copolymer (SAN), Acrylonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl methacrylate copolymer (SBMMA), styrene-maleic anhydride copolymer, styrene-methacrylic acid copolymer (SMA), amorphous polyamide, C ₄ -C ₈ alcohols, especially polyacrylates with identical or different alcohol radicals from the groups of butanol, hexanol, octanol and 2-ethylhexanol, polymethylmethacrylate (PMMA), methyl methacrylate-butyl acrylic Late copolymer, polyoxymethylene (POM), polyvinyl alcohol (PVAL), polyvinyl acetate (PVA), polyvinyl butyral (PVB), polycaprolactone (PCL), polyhydroxybutyric acid (PHB), polyhydride Includes oxyvaleric acid (PHV), polylactic acid (PLA), ethyl cellulose (EC), cellulose acetate (CA), cellulose propionate (CP) or cellulose acetate/butyrate (CAB).

Suitable further additives C4) are exemplified below as components C4 ₁ ) to C4 ₈ ).

The molding compositions of the invention may comprise, as component C4 ₁ ), 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, especially 0.1 to 1% by weight of lubricants, based on the thermoplastic molding composition.

Salts of Al, alkali metals or alkaline earth metals, or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably 12 to 44 carbon atoms, are preferred.

Metal ions are preferably alkaline earth metals and Al, with Ca or Mg being particularly preferred.

Preferred metal salts are Ca stearate and Ca montanate, and also Al stearate.

It is also possible to use any desired mixing ratio.

Carboxylic acids can be monobasic or dibasic. Examples that may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and especially preferably stearic acid, capric acid, and also montanic acid (30 to 40 mixture of fatty acids with carbon atoms).

Aliphatic alcohols can be monohydric to tetrahydric. Examples of alcohols include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, with glycerol and pentaerythritol being preferred.

Aliphatic amines can be monobasic to tribasic. Examples of these include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

It is also possible to use mixtures of various esters or amides, or mixtures of esters and amides, in any desired mixing ratio.

The molding compositions of the invention comprise, as component C4 ₂ ), a Cu(I) salt as stabilizer, preferably 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, especially 0.1 to 1% by weight, based on the thermoplastic molding composition. It may comprise a mixture of Cu(I) halides, especially alkali metal halides, preferably KI, especially in a ratio of 1:4.

Preferred salts of monovalent copper used are cuprous acetate, cuprous chloride, cuprous bromide and cuprous iodide. The material comprises copper in an amount of 5 to 500 ppm, preferably 10 to 250 ppm, based on the polyamide (i.e. polyamide blend according to the invention).

Advantageous properties are obtained especially when copper is present with its molecular distribution in the polyamide. This is achieved when a concentrate comprising a polyamide, comprising a monovalent copper salt and comprising an alkali metal halide in the form of a homogeneous solid solution is added to the molding composition. For example, a typical concentrate consists of 79 to 95% by weight of polyamide and 21 to 5% by weight of copper iodide or a mixture of copper bromide and potassium iodide. The copper concentration in the homogeneous solid solution is preferably 0.3 to 3% by weight, especially 0.5 to 2% by weight, based on the total weight of the solution, and the molar ratio of cuprous iodide to potassium iodide is 1 to 11.5, preferably 1. It is from 5 to 5.

According to one embodiment of the invention, the molding composition is free of copper iodide and potassium iodide and in particular free of metal halides.

Polyamides suitable for concentrates are homopolyamides and copolyamides, especially nylon-6 and nylon-6,6.

The molding composition of the present invention may comprise, as component C4 ₃ ), an oxidation retardant/antioxidant and/or a heat stabilizer. Examples of oxidation retardants/antioxidants and heat stabilizers include sterically hindered phenols and /or phosphites and amines (e.g., TAD), hydroquinone, aromatic secondary amines such as diphenylamine, various substituted members of these groups, and mixtures thereof.

Suitable sterically hindered phenols are, in principle, all compounds that have a phenol structure and have at least one bulky group on the phenol ring.

For example, it is preferred to use compounds of the formula:

In the above equation:

R ¹ and R ² are an alkyl group, a substituted alkyl group, or a substituted triazole group, where the radicals R ¹ and R ² may be the same or different, and R ³ is an alkyl group, a substituted alkyl group, an alkoxy group. , or a substituted amino group.

DE-A 27 02 661 (US-A 4 360 617) describes antioxidants of the type mentioned above as examples.

Another group of preferred sterically hindered phenols is provided by those derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.

Particularly preferred compounds of this class are those of the formula:

In the above formula, R ⁴ , R ⁵ , R ⁷ , and R ⁸ are, independently of each other, a C ₁ -C ₈ -alkyl group which may itself be substituted (at least one of which is a bulky group), and R ⁶ is a divalent aliphatic radical that has 1 to 10 carbon atoms and whose main chain may also have a CO bond.

Preferred compounds corresponding to these formulas are:

(Irganox ^® 245 from BASF SE)

(Irganox ^® 259 from BASF SE).

As examples of sterically hindered phenols the following should all be mentioned:

2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propio nate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hyde Roxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di -tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris (3,5 -di-tert-butyl-4-hydroxybenzyl)-benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy Benzyldimethylamine.

Compounds that have proven particularly effective and are preferably used include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4) -hydroxyphenyl)propionate (Irganox ^® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate], and also N, N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinamide ( ^Irganox® 1098), and the above-described ^Irganox® 245 product from BASF SE with particularly good suitability.

The amount comprised of antioxidant C4 ₃ ), which can be used individually or as a mixture, is 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, especially 0.1 to 1% by weight, based on the total weight of the molding composition.

In some cases, hindered phenols with more than one sterically hindered group in the ortho-position to the phenolic hydroxy group have proven to be particularly advantageous; This is especially true when evaluating colorfastness when stored in diffused light over long periods of time.

As component C4 ₄ ), the thermoplastic molding material generally contains 1.0 to 10.0% by weight, preferably 2.0 to 6.0, especially 3.0 to 5.0% by weight, based on the weight of the thermoplastic molding composition, of at least one flame retardant (other amounts are specified (if not mentioned) may be included.

A preferred flame retardant is phosphazene.

“Phosphazene” refers to a cyclic phosphazene of the general formula (IX):

In the above formula, m is an integer from 3 to 25, R ⁴ and R ^4' are the same or different, C ₁ -C ₂₀ -alkyl-, C ₆ -C ₃₀ -aryl-, C ₆ -C ₃₀ -arylalkyl - or represents C ₆ -C ₃₀ -alkyl-substituted aryl:

It should be understood as meaning a linear phosphazene of the general formula (X):

In the above formula, n represents ₃ to 1000 _, Indicates ₂ .

The production of these phosphazenes is described in EP-A 0 945 478.

A cyclic phenoxyphosphazene of the formula P ₃ N ₃ C ₃₆ of formula (XI): or

Linear phenoxyphosphazene according to formula (XII):

This is particularly desirable.

The phenyl radical may be optionally substituted. Phosphazenes in the context of the present application are described in Mark, J.E., Allcock, H.R., West, R., "Inorganic Polymers", Prentice Hall, 1992, pages 61 to 141.

Preferably, as component C4 ₄ ) a cyclic phenoxyphosphazene having at least 3 phenoxyphosphazene units is used. Corresponding phenoxyphosphazenes are described, for example, in paragraphs [0051] to [0053] of US 2010/0261818. In particular, reference may be made here to formula (I). The corresponding cyclic phenoxyphospharagens are further described in EP-A-2 100919, especially in paragraphs [0034 to [0038] thereof. The production may take place as described in paragraph [0041] of EP-A-2 100 919. In one embodiment of the invention, the phenyl group in the cyclic phenoxyphosphazene may be substituted by a C _1-4 -alkyl radical. Preference is given when pure phenyl radicals are involved.

Additional description of cyclic phosphazenes can be found in the literature ( Chemie Lexikon, 9 ^th ed., keyword “phosphazenes”). For example, production takes place via cyclophosphazene, which can be obtained from PCl ₅ and NH ₄ Cl, in which the chlorine group has been replaced by a phenoxy group by reaction with phenol.

Cyclic phenoxy phosphazene compounds are described, for example, in Allcock, H. R., “Phosphorus-Nitrogen Compounds” (Academic Press, 1972) and Mark, J. E., Allcock, H. R., West, R., “Inorganic Polymers” ( It can be produced as described in Prentice Hall, 1992).

Component C4 ₄ ) is preferably a mixture of cyclic phenoxyphosphazenes with 3 and 4 phenoxyphosphazene units. The weight ratio of rings containing three phenoxyphosphazene units to rings containing four phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may also be present, but in smaller quantities. A suitable cyclic phenoxyphosphazene is available from Fushimi Pharmaceutical Co., Ltd. under the name Rabitle® FP-100. It is a matte white/yellow solid with a melting point of 110°C and a phosphorus content of 13.4% and a nitrogen content of 6.0%. The proportion of rings containing three phenoxyphosphazene units is at least 80.0% by weight.

The thermoplastic molding material preferably contains 1.0 to 6.0% by weight, preferably 2.5 to 5.5% by weight, especially 3.0 to 5.0% by weight of at least one aliphatic or aromatic phosphoric acid or polyphosphoric acid as flame retardant, based on the amount of thermoplastic molding composition. Contains esters.

For this reason, solid, immobile phosphate esters are particularly preferred, having a melting point between 70°C and 150°C. This results in an easier product to meter and significantly less movement in the molding material. Particularly preferred examples are the phosphate esters PX-200 (CAS:139189-30-3 ^® ) commercially available from Daihachi or Sol-DP ^® from ICL-IP. Additional phosphate esters with appropriate substitution of the phenyl group may be considered to ensure that the desired melting range is achieved. Depending on the substitution pattern at the ortho or para position in the aromatic ring, the general structural formula is:

In the above equation,

R ¹ is H, methyl, ethyl or isopropyl, but is preferably H,

n is 0 to 7, but is preferably 0,

R ^2-6 is H, methyl, ethyl or isopropyl, but is preferably methyl. R ⁶ is preferably the same as R ⁴ and R ⁵ ,

m may but need not be equal and is between 1, 2, 3, 4 and 5, but is preferably 2;

R" can be H, methyl, ethyl or cyclopropyl, but is preferably methyl and H.

The PX-200 is provided as a specific example:

.

Particular preference is given when at least one aromatic ester of polyphosphoric acid is used. These aromatic polyphosphates are available, for example, from Daihachi Chemical under the designation PX-200.

As component C4 ₄ ), the thermoplastic molding material according to the invention contains 5.0 to 30.0% by weight, preferably 10.0 to 30.0% by weight, especially 12.0 to 20.0% by weight, for example about 16.0% by weight, based on the amount of thermoplastic molding composition. Weight percent of at least one metal phosphinate or phosphinic acid salt described below may be included as a flame retardant.

Examples of preferred flame retardants of component C4 ₄ ) are metal phosphinates derived from hypophosphorous acid. For example, metal salts of hypophosphorous acid with Mg, Ca, Al or Zn as metal can be used. Aluminum hypophosphite is particularly preferred here.

Also suitable are phosphinic acid salts of formula (I) or/and diphosphinic acid salts of formula (II) or polymers thereof:

In the above equation,

R ¹ , R ² are the same or different and represent hydrogen, linear or branched C ₁ -C ₆ -alkyl and/or aryl;

R ³ represents linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, -alkylarylene or -arylalkylene;

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogen base;

m is 1 to 4; n is 1 to 4; x is 1 to 4, preferably m is 3 and x is 3.

Preferably, R ¹ , R ² are the same or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl.

Preferably, R ³ is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; Methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; It represents phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene.

Particularly preferably, R ¹ , R ² are hydrogen, methyl or ethyl, M is Al, and Al hypophosphite is particularly preferred .

The production of the phosphinate is preferably carried out by precipitation of the corresponding metal salt from an aqueous solution. However, the phosphinates can also be precipitated in the presence of suitable inorganic metal oxides or sulfides as support materials (white pigments, for example TiO ₂ , SnO ₂ , ZnO, ZnS, SiO ₂ ). Therefore, it provides a surface modified pigment that can be used as a laser markable flame retardant for thermoplastic polyester.

Compared to hypophosphorous acid, one or two hydrogen atoms are replaced by phenyl, methyl, ethyl, propyl, isobutyl, isooctyl or the radical R'-CH-OH is replaced by R'-hydrogen, phenyl, tolyl. Preference is given when metal salts of phosphinic acid are used. The metal is preferably Mg, Ca, Al, Zn, Ti, or Fe. Aluminum diethylphosphinate (DEPAL) is particularly preferred.

For a description of the phosphinic or diphosphinic acid salts, reference may be made to DE-A 199 60 671 and also DE-A 44 30 932 and DE-A 199 33 901.

Additional flame retardants are, for example, halogen-containing flame retardants.

Suitable halogen-containing flame retardants are preferably brominated compounds such as brominated diphenyl ethers, brominated trimethylphenylindane (FR 1808 from DSB) tetrabromobisphenol A and hexabromocyclododecane.

Suitable flame retardants are preferably brominated compounds such as brominated oligocarbonates (BC 52 or BC 58 from Great Lakes) having the following structural formula:

.

Particularly suitable are polypentabromobenzyl acrylates with n>4 (e.g. FR 1025 from ICL-IP), which have the formula:

Preferred brominated compounds further include the oligomeric reaction products of tetra-bromobisphenol A with epoxides (n > 3) (e.g. FR 2300 and 2400 from DSB), having the formula:

Brominated oligostyrene, which is preferably used as a flame retardant, has an average degree of polymerization (number average) measured by vapor pressure osmosis in toluene of 3 to 90, preferably 5 to 60. Cyclic oligomers are likewise suitable. In a preferred embodiment of the invention, the brominated oligomeric styrene has the formula I shown below, wherein R represents hydrogen or an aliphatic radical, especially an alkyl radical, for example CH ₂ or C ₂ H ₅ and n represents a repeating chain Indicates the number of building blocks. R ¹ may be H, bromine or a fragment of a conventional free radical former:

The value of n may be 1 to 88, preferably 3 to 58. The brominated oligostyrene contains 40.0 to 80.0% by weight bromine, preferably 55.0 to 70.0% by weight. Products consisting primarily of polydibromostyrene are preferred. The substance can be dissolved without decomposition, for example in tetrahydrofuran. The materials can be prepared, for example, by ring bromination - optionally aliphatic hydrogenation - of styrene oligomers, such as those obtained by thermal polymerization of styrene (according to DT-OS 25,37,385) or by free radical oligomerization of suitable brominated styrenes. can be created by The production of flame retardants can also be carried out by ionic oligomerization of styrene and subsequent bromination. The amount of brominated oligostyrene required to impart flame retardancy to polyamide depends on the bromine content. The bromine content in the thermoplastic molding composition according to the present invention is preferably 2.0 to 30.0% by weight, more preferably 5.0 to 12.0% by weight, based on the amount of the thermoplastic molding composition.

Brominated polystyrene according to the invention is typically obtained by the process described in EP-A 047 549:

.

The commercially available brominated polystyrenes obtainable by this process are mainly ring-substituted tribromination products. n' (see III) generally has a value of 125 to 1500, corresponding to a molecular weight of 42500 to 235000, preferably 130000 to 135000.

The bromine content (based on the content of ring-substituted bromine) is generally at least 50.0% by weight, preferably at least 60.0% by weight and especially 65.0% by weight.

Commercially available powder products generally have a glass transition temperature of 160° C. to 200° C. and are available, for example, under the designation HP 7010 from Albemarle and Pyrocheck® PB 68 from Ferro Corporation.

Mixtures of brominated oligostyrene and brominated polystyrene can also be used in the molding material according to the invention, and the mixing ratio can be freely selected.

Chlorine-containing flame retardants are also suitable; Dechlorane plus from Oxychem is preferred.

Suitable halogen-containing flame retardants are preferably ring-brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxide oligomers or brominated bisphenol A polycarbonate.

In one embodiment of the invention, no halogen-containing flame retardants are used in the thermoplastic molding material according to the invention.

Flame-retardant melamine compounds suitable as component C4 ₄ ) in the context of the present invention are melamine compounds, which when added to polyamide molding materials filled with glass fibers reduce flammability and influence the fire behavior in a fire-retarding manner, complying with the UL 94 test and This results in improved properties in the glow wire test.

The melamine compound is selected, for example, from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon or melamine cyanurate or mixtures thereof.

Melamine cyanurates preferentially suitable according to the invention are preferably the reaction products of equimolar amounts of melamine (formula I) and cyanuric acid/isocyanuric acids (formula Ia and Ib):

This is obtained, for example, by reaction of aqueous solutions of the starting compounds at 90°C to 100°C. The commercially available product is a white powder with an average particle size d ₅₀ of 1.5 to 7 μm and a d ₉₉ value of less than 50 μm.

Further suitable compounds (sometimes also described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, primary phosphate, secondary phosphate and secondary pyrophosphate, melamine neopentyl glycol borate. According to the invention, the molding material preferably does not contain polymeric melamine phosphate (CAS No. 56386-64-2 or 218768-84-4).

This has a number average degree of condensation n of 20 to 200, and per mole of phosphorus atoms, melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, and diaminophenyl. It refers to a melamine polyphosphate salt of a 1,3,5-triazine compound selected from the group consisting of triazine with a 1,3,5-triazine content of 1.1 to 2.0 mol. It must be understood. Preferably, the n-value of these salts is generally from 40 to 150 and the ratio of 1,3,5-triazine compound per mole of phosphorus atoms is preferably from 1.2 to 1.8. Furthermore, the pH of the 10% by weight aqueous slurry of salt produced according to EP-B1 095 030 will generally be greater than 4.5, preferably at least 5.0. pH is typically determined by adding 25 g of salt and 225 g of clean water to a 300 ml beaker at 25°C, stirring the resulting aqueous slurry for 30 minutes, and then measuring the pH. The number average degree of condensation, the n-value mentioned above, can be determined by 31P solid state NMR. In the literature (J. R. van Wazer, C. F. Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956), the number of adjacent phosphate groups provides a clear distinction between orthophosphates, pyrophosphates and polyphosphates. It is disclosed that it provides a unique chemical shift that makes it possible.

Suitable guanidine salts are:

CAS number

guanidine carbonate 593-85-1

Primary Guanidine Cyanurate 70285-19-7

Primary Guanidine Phosphate 5423-22-3

secondary guanidine phosphate 5423-23-4

Primary guanidine sulfate 646-34-4

Secondary guanidine sulfate 594-14-9

Guanidine Pentaerythritol Borate Not applicable

Guanidine Neopentyl Glycol Borate Not applicable

and urea phosphate raw (green) 4861-19-2

Urea cyanurate 57517-11-0

Ameline 645-92-1

ammelite 645-93-2

melem 1502-47-2

melon 32518-77-7

In the context of the present invention, “compound” should be understood to mean, for example, benzoguanamine itself and its adducts/salts as well as nitrogen-substituted derivatives and adducts/salts thereof.

Also, ammonium polyphosphate (NH ₄ PO ₃ ) _n where n is about 200 to 1000, preferably 600 to 800 and tris(hydroxyethyl)isocyanurate (THEIC) of formula IV:

or with aromatic carboxylic acids Ar(COOH) _m , which may optionally exist in mixture with each other, where Ar represents a monocyclic, bicyclic or tricyclic aromatic six-membered ring system, and m is 2, It is 3 or 4.

Examples of suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, prehnitic acid, 1-naph. Included are acid acids, 2-naphthoic acid, naphthalenedicarboxylic acid, and anthracenecarboxylic acid.

The production is carried out according to the process of EP-A 584 567 by reaction of tris(hydroxyethyl)isocyanurate with an acid, an alkyl ester thereof or a halide thereof.

This reaction product is a mixture of monomeric and oligomeric esters that may be crosslinked. The degree of oligomerization is typically from 2 to about 100, preferably from 2 to 20. Preference is given to using mixtures of THEIC and/or its reaction products with phosphorus-containing nitrogen compounds, especially (NH ₄ PO ₃ ) _n or melamine pyrophosphate or polymeric melamine phosphate. For example, the mixing ratio of (NH ₄ PO ₃ ) _n to THEIC is preferably 90.0 to 50.0:10.0 to 50.0% by weight, especially 80.0 to 50.0:50.0 to 20.0% by weight, based on the mixture of these compounds.

Also suitable flame retardants are benzoguanidine compounds of formula (V):

In the above formulas, R, R' represent straight-chain or branched alkyl radicals having 1 to 10 carbon atoms, preferably hydrogen, especially their adducts with phosphoric acid, boric acid and/or pyrophosphoric acid.

Also preferred are allantoin compounds of formula VI:

wherein R, R' are as defined in formula (V) and are also salts thereof with phosphoric acid, boric acid and/or pyrophosphoric acid, and also salts with glycoluryl of formula (VII) or with the above-mentioned acids:

In the above formula, R is as defined in Formula V.

Suitable products are commercially available or can be obtained according to DE-A 196 14 424.

Cyanoguanidine (Formula VIII) usable according to the invention can be obtained, for example, by reacting calcium cyanamide with carbonic acid and dimerizing the resulting cyanamide at pH 9 to pH 10 to obtain cyanoguanidine. You can:

The commercially available product is a white powder with a melting point of 209°C to 211°C.

Particular preference is given to using melamine cyanurate (e.g. ^Melapur® MC25 from BASF SE).

It is also possible to use separate metal oxides such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides. For a description of penta-bromobenzyl acrylate and antimony trioxide or antimony pentoxide, see EP-A 0 624 626.

It is also possible to use phosphorus, for example red phosphorus, as component C4 ₄ ). Red phosphorus can be used, for example, in the form of a masterbatch.

Dicarboxylic acids of the formula:

In the above equation,

R ¹ to R ⁴ independently represent halogen or hydrogen, provided that at least one of the radicals R ¹ to R ⁴ represents halogen,

x is 1 to 3, preferably 1 or 2,

m is 1 to 9, preferably 1 to 3, 6, 9, especially 1 to 3,

n is 2 to 3,

M is an alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg.

Preferred dicarboxylic acid salts contain independently of each other Cl, bromine or hydrogen as radicals R ¹ to R ⁴ , and particularly preferably all radicals R ¹ to R ⁴ are Cl or/and Br.

Be, Mg, Ca, Sr, Ba, Al, Zn, and Fe are preferred as metal M.

These dicarboxylic acid salts are commercially available or can be prepared according to the process described in US 3,354,191.

Functional polymers can also be used as flame retardant components C4 ₄ ). These may be, for example, flame retardant polymers. Such polymers are described, for example, in US 8,314,202 and contain 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeat units. A further suitable functional polymer for increasing carbon retention is poly(2,6-dimethyl-1,4-phenyleneoxide) (PPPO).

As component C4 ₅ ), the thermoplastic molding composition may comprise 1 to 30% by weight, preferably 5 to 20, especially 6 to 10% by weight of at least one plasticizer.

In the context of the present invention, plasticizers are compounds capable of reducing the glass transition temperature of polyamides present in thermoplastic molding compositions. Suitable plasticizers are known to those skilled in the art. Examples include lactams, lactones, polyvinyl alcohol, sulfonamides such as N-(n-butyl)benzolsulfonamide and its derivatives, ethylene glycol such as tetraethylene glycol.

As component C4 ₆ ), the thermoplastic molding composition may comprise a UV stabilizer, generally in an amount of up to 2% by weight, based on the amount of thermoplastic molding composition. Examples of suitable UV stabilizers include various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.

As component C4 ₇ ), the thermoplastic molding composition may comprise a colorant. Substances that can be added as colorants are inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide, carbon black, and also organic pigments such as phthalocyanine, quinacridone, perylene, and also dyes such as anthraquinone.

As component C4 ₈ ), the thermoplastic molding composition may comprise a nucleating agent. Substances that can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and also preferably talc.

The polymer blends of the invention can be prepared by processes known per se, generally by mixing. The invention therefore relates to a process for preparing polymer blends according to the invention by mixing components A) and B).

The mixing of starting components A) and starting components B) can be carried out in conventional mixing devices known to those skilled in the art, such as screw-based extruders, especially twin-screw extruders, Brabender mixers or Banbury mixers. The resulting product can then be extruded. After extrusion, the extrudate can be cooled and pelletized.

Additionally, the thermoplastic molding compositions of the invention can be prepared by mixing the starting components A), B) and C) in a conventional mixing device such as a screw-based extruder, especially a twin-screw extruder, Brabender mixer or Banbury mixer, and then extruding them. It can be manufactured by a process known per se. After extrusion, the extrudate can be cooled and pelletized.

It is also possible to premix the individual components, for example components A) and B) to form the polymer blend according to the invention, and then add the remaining starting materials C) individually and/or likewise in the form of a mixture. .

Accordingly, the invention also relates to a process for producing a thermoplastic molding composition according to the invention by mixing component A), component B) or a polymer blend according to the invention with component C).

The mixing temperature is generally 230 to 320°C.

The inventive blends and inventive thermoplastic molding compositions are characterized in particular by one or more of the following properties: high stability to zinc chloride and blue addition, high heat distortion temperature, high tensile modulus in the dry and conditioned state, conditioning High stiffness in the wet state, low moisture absorption and high barrier to fuel. The inventive blends and inventive thermoplastic molding compositions are well suited for injection molding and sheet, foil, tube and pipe extrusion processes and are processable at mold temperatures typical for processing polyamides, for example.

The polymer blends and thermoplastic molding compositions of the invention are suitable for the manufacture of molded articles of any type, especially injection molded and blow molded parts and extruded parts (especially pipes and tubes).

Reinforced molding compositions comprising component C1) are particularly useful for injection molding. Accordingly, the preferred reinforced thermoplastic molding composition TM1 is particularly suitable for injection molding.

Unreinforced molding compositions without component C1) are particularly useful for extrusion, more preferably for sheet, foil, pipe or tube extrusion. Mentioned above are unreinforced thermoplastic molding compositions that are particularly suitable for extrusion.

Typical applications for the blends and thermoplastic molding compositions of the present invention include automotive, aerospace, electrical and industrial components that must withstand prolonged exposure to harsh chemicals and/or high temperatures.

Some specific examples are: Engineering plastics fields in contact with working fluids, such as cooling fluids, brake and clutch fluids, chemicals (plus blue), fuels and/or salts, especially in the automotive industry, for example in extrusion. Tubes (e.g. fluid pipes for fuel or cooling fluids in automobiles, cooling fluids for batteries in electric vehicles), mandrels and injection molded articles, such as functional parts for engine sensors (e.g. wheel speed sensors), pumps, connectors or injection or extrusion parts of fuel cells.

In the electrical and electronics sector, the blends and thermoplastic molding compositions of the present invention can be used to manufacture plugs, plug components, plug connectors, membrane switches, printed circuit board modules, microelectronic components, coils, I/O plug connectors, printed circuit boards ( Plug for printed circuit board (PCB), plug for flexible printed circuit (FPC), plug for flexible integrated circuit (FFC), high-speed plug connection, terminal strip, connector plug, device connector, cable harness (cable-harness) component, circuit mounting part, circuit mounting component. 3D injection molded circuit mountings, electrical connection elements and mechatronic components can be manufactured.

Possible uses of the blends and thermoplastic molding compositions of the invention in automotive and aerospace parts include, for example, dashboards, steering-column switches, seat components, headrests, center consoles, gearboxes. Components and interior materials for door modules, such as door handles, exterior-mirror components, windshield-wiper components, windshield-wiper protective housings, grilles, roof rails, sunroof frames, engine covers, Cylinder-head covers, intake pipes (especially intake manifolds), windshield wipers and also external body components and motor parts, fuel line connectors, coolant pumps, bushings, bearing pads in aircraft engines, charge air coolers. It is an exterior material for air coolers, resonators, engine cover components and heat shields, fuel cutoffs, water heater manifold valves, connectors, high voltage bushings, motor housings and headlight components.

Possible uses of the blends and thermoplastic molding compositions of the invention in the kitchen and household sector include producing components for kitchen appliances, such as fryers, smoothing irons, knobs, and also for garden applications. and in the leisure sector, for example in components for irrigation systems or garden equipment and door handles.

Accordingly, the invention also relates to the use of the polymer blends or thermoplastic molding compositions according to the invention for the production of molded articles, in particular for the production of extruded parts, injection molded parts and blow molded parts.

The invention also relates to molded and extruded parts, such as injection molded and blow molded, made from the polymer blends or thermoplastic molding compositions according to the invention. Examples of molded and extruded parts include molded articles, pipes, such as single- and multi-layer pipes, tubes, foils, and sheets.

Suitable and preferred applications and molded and extruded parts are mentioned above.

Figure 1: Save added in blue.
Figure 1 shows the results of storage tests in blue addition. In Figure 1, the tensile strength at break after 42 days of storage in the blue addition of Examples 1 to 3 was compared with Comparative Examples 1 and 2.
Curve 1 Comparative Example 1
Curve 2 Example 1
Curve 3 Example 2
Curve 4 Example 3
Curve 5 Comparative Example 2
Various times (days) are displayed on the horizontal axis (abscissa).
The vertical axis represents the tensile strength [%] when fracture is maintained relative to the initial value of [%].
Figure 2: Fuel penetration test results
Figure 2 shows the fuel penetration test results. Figure 2 shows the barrier to fuel of the inventive composition (inventive example 3) and comparative compositions (comparative examples 1 and 2) at 40°C. As reference/control, GF reinforced PA66 (Ultramid® A3WG6 bk564 from BASF SE) and GF reinforced PA6 (Ultramid® B3WG6 bk564 from BASF SE) were tested.
On the horizontal axis, different compositions and different solvents are mentioned.
1 Ultramid® A3WG6 bk564
2 Ultramid® B3WG6 bk564
3 Comparative Example 1
4 Example 3
5 Comparative Example 2
A EtOH
B hydrocarbon
C gun
The vertical axis represents the transmittance in [g/m ² *d] (where d means “day”).

Example

The following ingredients were used:

Component A)

AlCoPA 1: PA6/6.36; Ultramid® Flex F29 from BASF SE; (64% caprolactam, 6.3% HMD, 29.7% C36 partially unsaturated, MT: 199°C; relative viscosity: 2.8-3.0

AlCoPA2: PA6/6.36 from BASF SE; (64% caprolactam, 6.3% HMD, 29.7% C36 saturation; Ultramid® Flex F38 from BASF SE) MT: 199°C; Relative viscosity: 3.7-3.9

AlCoPA3: PA6/6.36 from BASF SE; (51.5% caprolactam, 8.5% HMD, 40.0% C36 saturation; from BASF SE) MT:199°C; Relative Viscosity: 3.7-3.9

Component B)

ArPA1: PA 6/6T (30/70) with a viscosity number VZ of 125 ml/g, measured in a solution of 0.5 weight strength in 96% weight strength sulfuric acid at 25°C according to ISO 307; MT (melting point) 294℃. (Ultramid® T315 from BASF SE)

ArPA2: PA6T/6I (70:30); ARLEN® 3000 from Mitsui Chemicals Europe GmbH; Has a viscosity number VZ of 90 ml/g, measured in a solution of 0.5 weight strength in 96% weight strength sulfuric acid at 25°C according to ISO 307, MT. 330℃, Tg: 125℃

ArPA3: PA6T/66 (70:30): ARLEN® C2000 from Mitsui Chemicals Europe GmbH; Has a viscosity number VZ of 100 ml/g, measured in a solution of 0.5 weight strength in 96% weight strength sulfuric acid at 25°C according to ISO 307, MT. 310℃, Tg: 125℃

AmArPA (comparative): amorphous PA6I/6T; Zytel® HTN301 from DuPont International Operations Sarl

Component C)

GF (glass fiber):

DS 1110 with a diameter of 10 μm (DS 1110-10N 4 mm from 3B-FIBREGLASS S.P.R.L)

CMB: 30 w% carbon black in LDPE

L1: Lubricant, calcium stearate flakes; Peter Greven GmbH & Co. LIGASTAR® CA 600 G from KG

L2: Lubricant, ACRAWAX® C BEADS

S1: Stabilizer, Irganox® 1098 ED from BASF SE

S2: Stabilizer, sodium hypophosphite monohydrate from OQEMA GmbH

S3: Stabilizer, OKAFLEX® EM from OKA-Tec Vertriebs GmbH

N1: Nucleating agent: TALKUM I.T. from Elementis Minerals B.V. Extra AW

IM1: Impact modifier: EXXELOR® VA 1801 from EXXONMOBIL PETROLEUM & CHEMICAL BV

IM2: Impact modifier: EXXELOR® VA 1803 from EXXONMOBIL PETROLEUM & CHEMICAL BV

Preparation of granules

The polymers shown in Tables 1 and 3 were compounded in the amounts specified in Tables 1 and 3 in a twin-screw extruder ZSK25 and extruded through a circular nozzle with a diameter of 4 mm while preserving the granules of the polymer composition. The amounts shown in Table 1 are in weight percent. The temperature profile of the extruder was adjusted to ensure that all polyamide was in a molten state. The temperatures are listed in Table 1, see Scheme 1, which shows a schematic diagram of the extruder with each segment G1-G11. Polyamides AlCoPA, ArPA, AmArPA and additives S, CMB and L (see description below) were administered through the feed zone. Glass fibers were administered through the side feeder of segment G5.

The granules were processed into specimens on a standard injection molding machine using the molds and melt temperatures listed in Table 1.

The tensile modulus of elasticity, tensile stress at break and tensile strain at break are determined according to ISO 527. Charpy (notch) impact resistance is determined according to ISO 179-2/1eU and ISO 179-2/1eAf respectively. Melting point and crystallization temperature are determined according to ISO 11357. All norms mentioned above and below refer to the version effective as of January 2021.

Scheme 1: Schematic diagram of the extruder

Table 1: Preparation and characterization of GF reinforced compounds based on aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA).

Table 2: Characteristics of GF enhanced blends

Stress crack resistance testing

The test fluid is an aqueous zinc chloride solution with a concentration of 50 w%. Tensile bars are dry (dry as formed) before testing. The tensile bar is clamped to a bending template with an edge fiber expansion of 2%. The surface of the bar is then wetted with a zinc chloride solution during the test and images are recorded to determine the time to failure. The test runs until it fails, or stops after 3 days if no failure occurs. GF reinforced PA66 (Ultramid® A3EG5 sw564 (Ult. A3EG5 sw564) from BASF SE) and GF reinforced PA6 (Ultramid® B3EG6 sw564 (Ult. B3EG6 s4564) from BASF SE) with comparable tensile modulus as reference/control. was tested.

Table 2a: Zinc chloride stress cracking resistance test results

Fuel penetration test (Figure 2)

Working steps: Injection molding of test specimens (plaques 150 x 150 x 1 mm). Accelerated conditioning of specified E10 fuel at 40°C. Migration test at 40°C and GC analysis of permeate (2 plaques per sample). As reference/control, GF reinforced PA66 (Ultramid® A3WG6 bk564 from BASF SE) and GF reinforced PA6 (Ultramid® B3WG6 bk564 from BASF SE) were tested.

2) Preparation and characterization of aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA) blends

Table 3: Blends of aliphatic copolyamide (AlCoPA) aromatic polyamide (ArPA)

* Material sticks to the mold

Table 4: Properties of blends of aliphatic copolyamide (AlCoPA) aromatic polyamide (ArPA)

3) Preparation and characterization of impact modified compounds based on aliphatic copolyamide (AlCoPA) and aromatic polyamide (ArPA)

Impact modifier IM1 of Comparative Example 4 and Inventive Example 6 was administered along with other ingredients through the feeding zone. In Comparative Examples 5 and 6 and Inventive Examples 7 to 12, the impact modifier IM2 was administered via the side feeder in segments G 7 to 12. Shock modifier IM2 was administered through the lateral feeder in segment G8.

Table 5: Impact modified compounds of aliphatic copolyamide (AlCoPA) aromatic polyamide (ArPA) blends

Table 6: Properties of impact modified compounds of aliphatic copolyamide (AlCoPA) aromatic polyamide (ArPA) blends

Table 7: Pipe Compression

The material was extruded into a 12 mm pipe through a nozzle with a diameter of 16.8 mm and a core of 13.2 mm.

Reinforced thermoplastic molding composition

Table 1 describes the preparation of glass fiber reinforced compounds. The stiffness (tensile modulus and tensile strength) of the conditioned state increases significantly (Examples 1 to 3), while the stability (stress crack resistance) to zinc chloride remains high (see Table 3). Surprisingly, compositions comprising blends of semi-crystalline, semi-aromatic polyamides and aliphatic copolyamides according to the present invention can be obtained by combining pure aliphatic copolyamides (Comparative Example 1) and blends of aliphatic copolyamides and amorphous, semi-aromatic polyamides. The comprising composition (Comparative Example 2) exhibits an increased barrier to fuels not shown (see Figure 2). Examples 1 to 3 and Comparative Example 2 have higher tensile strength at break after 42 days of storage in blue color compared to Comparative Example 1 (Figure 1). Additionally, the blend of aliphatic copolyamide and polyamide 6T/66 (Example 3) further exhibits increased heat distortion temperatures (HDTA and HDTB). When using amorphous semi-aromatic polyamide (Comparative Example 2), the heat distortion temperature is further reduced (see Table 2). Although the melt temperatures of the semi-crystalline, semi-aromatic polyamides of Examples 2 and 3 exceed 300°C, the resulting compounds are processable by injection molding with a maximum melt temperature of 300°C.

In summary, it has high stability to zinc chloride, blue addition, high heat distortion temperature, high stiffness in the conditioned state, low moisture absorption, and high barrier to fuels that can be processed by injection molding with a melt temperature below 300°. It was possible to obtain reinforced thermoplastic compositions based on the blends of the invention. This property profile offers a wide range of applications in the engineering plastics field mentioned above.

In the first heating curve of the DSC curve of Example 3, the individual melting points of the aliphatic copolyamide (AlCoPA) can be observed at 195.4 ° C. and the melting points of the semi-crystalline, semi-aromatic polyamide (ArPA3) at 308.77 ° C. . Surprisingly, no significant trans-amination occurred during compounding. In the secondary heating curve after the sample was held in the molten state for 5 min, a new melting peak occurred at 174.95 °C, which was derived from the trans It belongs to amination products. Due to these observations, it is possible to perform targeted control of material properties in the injection molding stage.

Table 4 describes the preparation of the inventive polymer blends (Examples 4 and 5) of an aliphatic copolyamide (AlCoPA) and a semi-crystalline, semi-aromatic polyamide (ArPA). The blend was processed via injection molding and compared to Comparative Example 3, which does not contain semi-crystalline, semi-aromatic polyamide. Comparative Example 3 could hardly be processed in injection molding because the material stuck to the mold surface. As a result, it is necessary to work at very low mold temperatures (40°C). In contrast, inventive examples 4 and 5 could be processed at higher mold temperatures (80° C.) typical for polyamide processing. Examples 4 and 5 of the present invention had higher tensile modulus in the dry and conditioned state, and heat distortion temperatures (HDTA and HDTB) were significantly increased compared to Comparative Example 3.

I. Impact modified thermoplastic molding composition

Table 5 describes the preparation of impact modified thermoplastic molding compositions in one compounding step. Comparative Examples 4 and 5 presented problems during the granulation process. The granules were stacked on top of each other and it was almost impossible to cut them. Inventive Example 6 shows increased tensile modulus and increased HDTB value in the conditioned state compared to Comparative Example 5. Comparative Example 4 and Inventive Example 6 were extruded into 12 mm pipes. Inventive Example 6 can be extruded below the melting temperature of the semi-crystalline, semi-aromatic polyamide ArPA1 of 210°C. The pipe made from Inventive Example 6 had a smooth opaque surface, while the pipe from Comparative Example 4 was difficult to make. Material accumulated in the nozzle, making it impossible to manufacture a pipe with a smooth surface.

Claims (15)

As a polymer blend,
a) more than 50% by weight to 99% by weight of at least one aliphatic copolyamide as component A);
b) 1% to less than 50% by weight of at least one semicrystalline, semiaromatic or aromatic polyamide as component B
Includes;
A polymer blend wherein the total weight percent of components A and B is 100 weight percent. 2. The polymer blend of claim 1, wherein the polyamide of component B has a melting point greater than 250°C. 3. The polymer blend of claim 1 or 2, wherein the polyamide of component B is semi-aromatic. 4. The polymer blend of any one of claims 1 to 3, wherein the polyamide of component B is a copolyamide. 5. The polymer blend of any one of claims 1 to 4, wherein the polyamide of component A has a melting point of less than 220°C. 6. The polyamide according to any one of claims 1 to 5, wherein the polyamide of component A preferably consists of
A') 15% to 84% by weight of at least one lactam,
B') The following ingredients
B1') at least one C ₃₂ -C ₄₀ -dimer acid, and
B2') at least one C ₄ -C ₁₂ diamine
16% to 85% by weight of a monomer mixture (M) comprising
It is a copolyamide prepared by polymerization of,
A polymer blend wherein the weight percentages of components A') and B') are in each case based on the sum of the weight percentages of components A') and B'). 7. The monomer mixture (M) according to claim 6, wherein the monomer mixture (M) contains from 45 mol% to 55 mol% of component B1') and from 45 mol% to 55 mol%, based in each case on the sum of the mole% of components B1') and B2'). % of component B2'). Thermoplastic molding composition comprising a polymer blend according to any one of claims 1 to 7 and at least one additional substance C). The thermoplastic molding composition according to claim 8, comprising as additional substance C at least one fibrous and/or particulate filler as component C1). 10. Thermoplastic molding composition according to claims 8 or 9, comprising as additional substance C at least one impact modifier as component C2). 11. The method according to any one of claims 8 to 10, comprising as further substance C at least one thermoplastic polymer distinct from components A), B), C2) as component C3) and distinct from optional further additives. Thermoplastic molding composition. A process for preparing a polymer blend according to any one of claims 1 to 7 by mixing component A with component B. A process for producing a thermoplastic molding composition according to any one of claims 8 to 11 by mixing components A, B or a polymer blend according to any one of claims 1 to 7 with at least one further material C. . Polymer blends according to any one of claims 1 to 7 or thermoplastics according to any of claims 8 to 11 for the production of molded and extruded parts, in particular molded articles, pipes, sheets, foils and tubes. Uses of molding compositions. Molded or extruded parts, preferably molded articles, pipes, sheets, foils, made from the polymer blend according to any one of claims 1 to 7 or the thermoplastic molding composition according to any one of claims 8 to 11. Or tube.